New developments in first-principles excited-state dynamics simulations: unveiling the solvent specificity of excited anionic cluster relaxation and electron solvation

Mak, Chun C.; Peslherbe, Gilles H.

doi:10.1080/08927022.2014.945083

Cited by 4 publications

(2 citation statements)

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“…This new structure is clearly unfavorable for the ground state of the system, which is lifted by 4.4 eV for the chosen example. The excitation of F – in solution follows probably this route in the very beginning of the relaxation because the closest hydrogen atoms are no longer attracted by the neutral F atom and tend to repeal each other. ,− As observed for I – (H 2 O) n =3 , the kinetic energy released in this process is however far sufficient to overcome the small energy barrier on the order of 0.13 eV necessary to transfer a hydrogen atom to the fluorine and thus to create a tightly bound HF molecule nearby a OH radical. Once relaxed, this latter arrangement is located 3.4 eV below the excited state at the ground-state geometry.…”

Section: Energy Landscapementioning

confidence: 97%

“…Regarding halides embedded in water clusters, excited state studies have been performed in the case of I – (H 2 O) n . In particular, ab initio molecular dynamics simulations based either on RASSCF , or on DFT , calculations have been used to follow the CTTS state relaxation characterized by iodine atom detachment from the negatively charged water cluster. In solution, the relaxation of Cl – and I – CTTS states has been investigated by means of model potential techniques. , …”

Section: Introductionmentioning

confidence: 99%

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RASPT2 Analysis of the F^–(H₂O)_n=1–7 and OH^–(H₂O)_n=1–7 CTTS States

2018

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We analyze the electronic structure of the lowest excited states of the F(HO) and OH(HO) anionic clusters in the framework of RASPT2 theory. At the ground-state geometry, these clusters can bind the excess electron in the first excited singlet and triplet states for n ≥ 3 for F and n ≥ 2 for OH. The geometry relaxation of the F(HO) clusters in their lowest-energy triplet state produces two series of minima. A first series is made of a F radical weakly bound to a negatively charged water cluster to form F-(HO) . A second series associated with hydrogen transfer from a water molecule to the fluorine atom is built on a HF molecule and a OH radical bound to a negatively charged water cluster to form OH-HF-(HO) . This second series provides the lowest-energy isomers of F(HO) for the excited state. These two series of minima are inherited from the neutral fluorine water cluster structure only weakly perturbed by the excess electron. They are similar to the OH(HO) isomers obtained for the lowest-energy triplet state, which are also made of a neutral OH radical inserted in the water molecule network of a (HO) cluster. For all of these clusters in the lowest-energy excited state, the excess electron is localized outside of the cluster near unbound hydrogen atoms. Its binding energy is well correlated to the electric dipole of the cluster, and a lower limit of 4.1 D is necessary to bind it to the cluster. The two series of F(HO) isomers offer two very different routes for geminate recombination observed in water solutions. Our calculation suggests that the recombination takes place with the OH radical left after hydrogen transfer rather than with the F radical.

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Section: Energy Landscapementioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

RASPT2 Analysis of the F^–(H₂O)_n=1–7 and OH^–(H₂O)_n=1–7 CTTS States

2018

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Charge‐transfer‐to‐solvent absorption spectra of I⁻(H₂O)_3–5 at a finite temperature via simulation

Chiou

Sheu

2017

Int J of Quantum Chemistry

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Ground‐state equilibrium Born–Oppenheimer molecular dynamics on I−(H2O)3–5 clusters at ∼200 K are performed to sample configurations for calculating the charge‐transfer‐to‐solvent (CTTS) absorption spectra for these clusters. When there are more water molecules in clusters, the calculated CTTS spectra are found to become more intense with the absorption maxima shifting to higher energies, which is in agreement with experimental results. In addition, compared with the findings for optimized structures, the absorption energies of the iodide 5p orbitals are red‐shifted at ∼200 K because, on average, the distances between the iodide and the dangling hydrogen atoms are increased at finite temperatures which weakens the interactions between the iodide and water molecules in the clusters. Moreover, the number of ionic hydrogen bonds in the clusters are also reduced. However, it is found that all dangling hydrogen atoms must be considered to obtain a good correlation between the CTTS excitation energy and the average distance between the iodide and the dangling hydrogen atoms, which indicates the existence of the strong interactions of the CTTS electron with all of the dangling hydrogen atoms.

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Ultraviolet charge-transfer-to-solvent spectroscopy of halide and hydroxide ions in subcritical and supercritical water

Marin

Janik

Bartels

2019

Phys. Chem. Chem. Phys.

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New developments in first-principles excited-state dynamics simulations: unveiling the solvent specificity of excited anionic cluster relaxation and electron solvation

Cited by 4 publications

References 62 publications

RASPT2 Analysis of the F^–(H₂O)_n=1–7 and OH^–(H₂O)_n=1–7 CTTS States

RASPT2 Analysis of the F^–(H₂O)_n=1–7 and OH^–(H₂O)_n=1–7 CTTS States

Charge‐transfer‐to‐solvent absorption spectra of I⁻(H₂O)_3–5 at a finite temperature via simulation

Ultraviolet charge-transfer-to-solvent spectroscopy of halide and hydroxide ions in subcritical and supercritical water

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New developments in first-principles excited-state dynamics simulations: unveiling the solvent specificity of excited anionic cluster relaxation and electron solvation

Cited by 4 publications

References 62 publications

RASPT2 Analysis of the F–(H2O)n=1–7 and OH–(H2O)n=1–7 CTTS States

RASPT2 Analysis of the F–(H2O)n=1–7 and OH–(H2O)n=1–7 CTTS States

Charge‐transfer‐to‐solvent absorption spectra of I−(H2O)3–5 at a finite temperature via simulation

Ultraviolet charge-transfer-to-solvent spectroscopy of halide and hydroxide ions in subcritical and supercritical water

Contact Info

Product

Resources

About

RASPT2 Analysis of the F^–(H₂O)_n=1–7 and OH^–(H₂O)_n=1–7 CTTS States

RASPT2 Analysis of the F^–(H₂O)_n=1–7 and OH^–(H₂O)_n=1–7 CTTS States

Charge‐transfer‐to‐solvent absorption spectra of I⁻(H₂O)_3–5 at a finite temperature via simulation